CN117447996B - CsPbCl 3 :Mn 2+ Method for detecting 4-nitrophenol in water by PEG nanocrystalline - Google Patents
CsPbCl 3 :Mn 2+ Method for detecting 4-nitrophenol in water by PEG nanocrystalline Download PDFInfo
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- 238000001514 detection method Methods 0.000 claims abstract description 18
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Abstract
The invention discloses a CsPbCl 3 :Mn 2+ Method for detecting 4-nitrophenol in water by PEG nanocrystalline, (1) PbCl 2 、MnCl 2 Dissolving polyethylene glycol in DMF, adding oleic acid, oleylamine and concentrated HCl, stirring to obtain pale green precursor solution, adding the precursor solution into mixed solution of cesium acetate, oleic acid and xylene under stirring, centrifuging after reaction, adding toluene into the precipitate, dispersing with ultrasound, centrifuging, and collecting the precipitate to obtain CsPbCl 3 :Mn 2+ PEG nanocrystals; (2) CsPbCl 3 :Mn 2+ PEG nanocrystals were dispersed in deionized water, and then the 4-nitrophenol was detected under 250nm fluorescence excitation after dilution of the nanocrystal solution into a dilute hydrochloric acid solution at pH 1. The invention leads CsPbCl with double emission peaks 3 :Mn 2+ The perovskite quantum dots are coated in polyethylene glycol to synthesize nano crystals with better water stability, the nano crystals are used as fluorescent probes to be applied to the detection of 4-NP in water, the selectivity is good,in the presence of other interfering ions, the fluorescence intensity only shows better responsiveness to 4-NP.
Description
Technical Field
The invention belongs to the technical field of photoluminescent fluorescent probes, relates to application of polymer PEG coated perovskite quantum dots in quantitative detection of 4-NP, and particularly relates to CsPbCl 3 :Mn 2+ PEG nanocrystalline method for detecting 4-nitrophenol in water.
Background
4-nitrophenol (4-NP) is used as a fine chemical intermediate and is widely applied to the fields of pesticides, medicines, dyes and the like. However, 4-NP is also an intractable environmental pollutant and hazardous waste. 4-NP has good chemical stability and high water solubility due to its high conjugated structure and hydroxyl group, and gradually accumulates in ambient water. It has been reported that 4-NP can pose a serious threat to human health and that acute inhalation or misingestion can cause headache, somnolence, nausea, resulting in damage to the cardiovascular, renal and central nervous system. Thus, the use of 4-NPs should be strictly controlled and supervised. Its maximum allowable level in drinking water is currently specified to be 60 mug/L (0.43 mug). In addition, 4-NP is highly stable and poorly biodegradable, and is extremely difficult to remove from contaminated wastewater and soil. Therefore, it is of great importance to develop a simple, sensitive and efficient method for monitoring 4-NP in an environment. At present, many strategies for detecting 4-NPs have been devised, including liquid chromatography-mass spectrometry tandem, electrochemistry, capillary electrophoresis, photoelectrochemistry, high performance liquid chromatography, fluorescence spectrometry, and the like. Compared with other methods, the fluorescence method is receiving more and more attention due to the advantages of simple operation, high response speed, high sensitivity, high selectivity and the like. Various fluorescence methods for detecting 4-NP have been established, including inorganic nanomaterials, organic fluorescent dyes, semiconductor Quantum Dots (QDs), metal-organic frameworks, and other fluorescent materials with excellent physical and chemical properties. Perovskite-based materials exhibit excellent fluorescence properties, high fluorescence quantum yields, compared to other fluorescent materials. Thus, we chose to use perovskite-based fluorescent probes for 4-NP detection. In recent years, csPbX 3 (x=cl, br, I) perovskite nanomaterial consists ofThe fluorescent dye has excellent photoelectric properties such as high photoluminescence quantum yield (PLQYs), extremely narrow half-peak width, low reaction temperature, low cost, adjustable emission wavelength of the whole visible spectrum and the like, and has great potential in various photoelectric devices, fluorescent probes and the like. However, due to the low energy of formation and ionic nature of perovskite materials, perovskite is extremely sensitive to humidity, light and temperature, and its instability greatly limits its application in many fields, in particular in biochemical detection. Therefore, improving the stability of perovskite materials has been the main research direction in recent years.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provides a CsPbCl 3 :Mn 2+ Method for detecting 4-nitrophenol by PEG nanocrystalline, the invention leads CsPbCl with double emission peaks 3 :Mn 2+ Perovskite quantum dots are coated in amphiphilic polyethylene glycol with good biocompatibility, and CsPbCl with good synthetic water stability is synthesized 3 :Mn 2+ PEG nanocrystalline, csPbCl 3 :Mn 2+ PEG nanocrystals as fluorescent probes are used for detection of 4-NP in water.
The technical scheme adopted for solving the technical problems of the invention is as follows:
CsPbCl 3 :Mn 2+ The method for detecting 4-nitrophenol by PEG nanocrystalline comprises the following specific processes: (1) Ligand-assisted reprecipitation method for synthesizing CsPbCl 3 :Mn 2+ PEG nanocrystals: pbCl is added 2 、MnCl 2 And polyethylene glycol PEG dissolved inN,NAdding oleic acid, oleylamine and concentrated HCl into dimethylformamide, stirring to obtain pale green precursor solution, adding the precursor solution into cesium acetate, oleic acid and xylene mixed solution under stirring, centrifuging after reaction to remove supernatant, adding toluene into precipitate, dispersing with ultrasound, centrifuging, and collecting precipitate to obtain CsPbCl 3 :Mn 2+ PEG nanocrystals; (2) The obtained CsPbCl 3 :Mn 2+ PEG nanocrystals were dispersed in deionized water, followed by CsPbCl 3 :Mn 2+ Diluting PEG nanocrystalline solution into hydrochloric acid diluted solution with pH of 1, and fluorescence exciting at 250nmDetecting 4-nitrophenol by the initiation.
CsPbCl described above 3 :Mn 2+ The method for detecting 4-nitrophenol by PEG nanocrystalline comprises the following specific steps: (1) Will be 0.25mmolPbCl 2 、0.25mmolMnCl 2 And 40mg polyethylene glycol PEG dissolved in 5mLN,NAdding 0.5mL of oleic acid and 0.5mL of oleylamine into dimethylformamide, adding 0.5mL of concentrated HCl, stirring to obtain a pale green precursor solution, injecting 1mL of precursor solution into a mixed solution containing 0.05mmol of cesium acetate, 1mL of oleic acid and 5mL of xylene under stirring, reacting for 30-38s, irradiating with an ultraviolet lamp to observe bright orange fluorescence, centrifuging the obtained sample, removing supernatant, adding 3mL of toluene into the precipitate, ultrasonically dispersing, and centrifuging to collect the precipitate to obtain CsPbCl 3 :Mn 2+ PEG nanocrystals; (2) CsPbCl to be collected 3 :Mn 2 + PEG nanocrystals were dispersed in 2mL deionized water to form CsPbCl 3 :Mn 2+ 100 mu L CsPbCl is measured out of PEG nanocrystalline aqueous solution 3 :Mn 2+ The PEG nanocrystalline aqueous solution is diluted into 3mL of hydrochloric acid diluted solution with pH value of 1 for detecting 4-nitrophenol in water.
In the step (1), 1mL of the precursor solution was injected into a mixed solution containing 0.05mmol of cesium acetate, 1mL of oleic acid and 5mL of xylene with stirring at 1700-2000 r/min.
And (3) centrifuging the sample obtained in the step (1) at 9000-10000r/min for 10-15min.
In the step (1), 3mL of toluene is added into the sediment, ultrasonic dispersion is carried out by using ultrasonic wave with the frequency of 40KHz, and the sediment is collected by centrifugation for 10-15min at 9000-10000 r/min.
CsPbCl in the step (2) 3 :Mn 2+ The concentration range of the 4-nitrophenol detected by the PEG nano-crystal is 0.00029-0.40876mmol/L.
CsPbCl of the invention 3 :Mn 2+ Perovskite quantum dots are prepared by Mn 2+ Substituted Pb 2+ Can significantly change CsPbCl 3 The optical property of the perovskite quantum dot greatly improves the PL quantum yield. CsPbCl 3 ：Mn 2+ PQDs exhibit dual emission under UV excitation, two emissionsThe peaks are at 400nm and 590nm, respectively, which are attributable to CsPbCl 3 Band edge exciton emission and Mn of (2) 2+ d-d transition [ ] 4 T 1 → 6 A 1 A transition). CsPbCl under ultraviolet excitation 3 :Mn 2+ Perovskite quantum dots exhibit orange-red fluorescence, mainly derived from semiconductor substrates to Mn 2+ Energy transfer of (c) leading to Mn 2+ Ion at 4 T 1 And 6 A 1 the transition between the energy levels produces radiant luminescence.
CsPbCl 3 :Mn 2+ Polyethylene glycol (PEG) of PEG nanocrystalline is a synthetic polymer material composed of two methylene groups and one oxygen atom repeated on the main chain, and can be dissolved in water and some organic solvents. In addition, it can be connected with other molecules or surfaces through chemical reaction to form a biocompatible protective film, which not only can reduce the rejection opportunity of biological systems to materials, but also can greatly reduce the adsorption of proteins, cells and bacteria on the surfaces of the materials. The hydrophilicity and high biocompatibility of PEG, as well as their gentle and clear chemical reaction properties, make it an ideal coupling or bonding agent from molecule to molecule or from molecule to molecule and surface. PEG was chosen as CsPbCl 3 :Mn 2+ The protective layer of the perovskite quantum dot can effectively avoid the damage of the external environment, so that the prepared CsPbCl 3 :Mn 2+ PEG nanocrystals have excellent water stability and water solubility. In addition, absorption spectrum of 4-NP at 380nm and CsPbCl3:Mn 2+ PEG nanocrystals have partial spectral overlap in the 400nm center emission spectrum, resulting in CsPbCl 3 :Mn 2+ The quantum dots undergo fluorescence quenching by a Fluorescence Resonance Energy Transfer (FRET) mechanism.
The beneficial effects of the invention are as follows: 1. CsPbCl prepared by adopting polyethylene glycol with good biocompatibility as surface coating material 3 :Mn 2+ PEG nanocrystals were good in water solubility. PEG coating greatly improves CsPbCl 3 :Mn 2+ Fluorescence stability of perovskite quantum dots in water. CsPbCl 3 :Mn 2+ After the PEG nanocrystals were stored in water for 25 days, the fluorescence intensity was still above 40% of the initial intensity. 3. By CsPbCl 3 :Mn 2+ Relationship I between fluorescence spectrum relative intensity of PEG nanocrystalline under 250nm excitation light and 4-NP concentration 0 /I (400nm) =1.0683+4.2545C 4-NP And I 0 /I (590nm) =1.1235+5.3868C 4-NP Can be applied to quantitative detection of 4-NP concentration in water. 4. The detection limit was low, and the detection Limit (LOD) values calculated by 3 sigma/K formula were 0.40563. Mu.M (400 nm) and 0.36362. Mu.M (590 nm), respectively, which were lower than the maximum allowable concentration of 4-NP in drinking water by 0.43. Mu.M. 5. Good selectivity, csPbCl in the presence of other interfering ions 3 :Mn 2+ The fluorescence intensity of the PEG nanocrystalline only shows good response to 4-NP. CsPbCl 3 :Mn 2+ The preparation method of the PEG nanocrystalline is green and economical, and provides a novel method for the application of perovskite quantum dots in 4-NP detection in water.
Drawings
FIG. 1 is a CsPbCl of the invention 3 :Mn 2+ TEM image of PEG nanocrystals under different scales;
FIG. 2 is a CsPbCl of the invention 3 :Mn 2+ Stability of PEG nanocrystals in Water, FIG. a is CsPbCl 3 :Mn 2+ Photographs taken of PEG nanocrystals under natural light, panels b, c, and d were CsPbCl after 1 day, 12 days, and 33 days, respectively, of storage in water 3 :Mn 2+ PEG in ultraviolet (250 nm) light emission photograph;
FIG. 3 shows the dispersion of CsPbCl in accordance with the present invention 3 :Mn 2+ Adding 4-NP with different concentrations into the aqueous solution of PEG nanocrystalline to react with the 4-NP, and monitoring the obtained fluorescence spectrogram under 250nm excitation;
FIG. 4 is a CsPbCl of the invention 3 :Mn 2+ Fluorescence quenching value (I) of PEG nanocrystals at 400nm and 590nm wavelengths 0 A Sternee-Volmer plot between I) and 4-NP concentrations;
FIG. 5 is a graph showing CsPbCl of the 4-NPs of this invention at the same concentration of 7.5 μg/mL as interfering ions 3 :Mn 2+ Selectivity of PEG nanocrystals versus 4-NP and interfering ions.
Detailed Description
Example 1
CsPbCl 3 :Mn 2+ The method for detecting 4-nitrophenol in water by PEG nanocrystalline comprises the following steps:
(1) Ligand-assisted reprecipitation method for synthesizing CsPbCl 3 :Mn 2+ PEG nanocrystalline
PbCl is added 2 (0.25mmol)、MnCl 2 (0.25 mmol) and polyethylene glycol PEG (40 mg) were dissolved in 5mLN,NTo dimethylformamide, oleic acid (0.5 mL) and oleylamine (0.5 mL) were added, and finally concentrated HCl (0.5 mL) was added and stirred for 10min to give a pale green precursor solution, 1mL of the precursor solution was poured into a mixed solution containing cesium acetate (0.05 mmol), oleic acid (1 mL) and xylene (5 mL) with vigorous stirring (1700 r/min), a white precipitate appeared immediately, and after 38s of reaction, bright orange fluorescence was observed by irradiation with an ultraviolet lamp; centrifuging the obtained sample at 9000r/min for 10min, removing supernatant, adding toluene (3 mL) into the precipitate, performing ultrasonic dispersion (frequency 40 KHz), centrifuging at 10000r/min for 10min, and collecting precipitate to obtain CsPbCl 3 :Mn 2+ PEG nanocrystals; finally, the sample is ultrasonically dispersed in 2mL of deionized water for characterization.
（2）CsPbCl 3 :Mn 2+ Use method of PEG nanocrystalline quantitative detection of 4-NP in water
CsPbCl to be collected 3 :Mn 2+ PEG nanocrystals were dispersed in 2mL deionized water to form CsPbCl 3 :Mn 2+ PEG nanocrystalline aqueous solution, precisely 100 mu LCsPbCl 3 :Mn 2+ PEG nanocrystalline aqueous solution and diluted to 3mL, pH 1 hydrochloric acid diluted solution, and with different concentrations of 4-NP solution (0.00029 mmol/L, 0.00071mmol/L, 0.00359mmol/L, 0.00719mmol/L, 0.01438mmol/L, 0.02875mmol/L, 0.04633mmol/L, 0.06387mmol/L, 0.08137mmol/L, 0.11628mmol/L, 0.15105mmol/L, 0.20295mmol/L, 0.25455mmol/L, 0.30586mmol/L, 0.34023mmol/L, 0.40876 mmol/L) for 1min, under 250nm excitation fluorescence emission spectrum was recorded.
Example 2
CsPbCl 3 :Mn 2+ The method for detecting 4-nitrophenol by PEG nanocrystalline comprises the following steps:
（1）ligand-assisted reprecipitation method for synthesizing CsPbCl 3 :Mn 2+ PEG nanocrystalline
PbCl is added 2 (0.25mmol)、MnCl 2 (0.25 mmol) and polyethylene glycol PEG (40 mg) were dissolved in 5mLN,NTo dimethylformamide, oleic acid (0.5 mL) and oleylamine (0.5 mL) were added, and finally concentrated HCl (0.5 mL) was added and stirred for 20min to give a pale green precursor solution, 1mL of the precursor solution was poured into a mixed solution containing cesium acetate (0.05 mmol), oleic acid (1 mL) and xylene (5 mL) with vigorous stirring (2000 r/min), a white precipitate appeared immediately, and after 30s of reaction, bright orange fluorescence was observed by irradiation with an ultraviolet lamp; centrifuging the obtained sample at 10000r/min for 15min, removing supernatant, adding toluene (3 mL) into the precipitate, performing ultrasonic dispersion (frequency 40 KHz), centrifuging at 9000r/min for 15min, and collecting precipitate to obtain CsPbCl 3 :Mn 2+ PEG nanocrystals; finally, the sample is ultrasonically dispersed in 2mL of deionized water for characterization.
（2）CsPbCl 3 :Mn 2+ Use method of PEG nanocrystalline quantitative detection of 4-NP in water
CsPbCl to be collected 3 :Mn 2+ PEG nanocrystals were dispersed in 2mL deionized water to form CsPbCl 3 :Mn 2+ PEG nanocrystalline aqueous solution, precisely 100 mu LCsPbCl 3 :Mn 2+ PEG nanocrystalline aqueous solution and diluted to 3mL, pH 1 hydrochloric acid diluted solution, and with different concentrations of 4-NP solution (0.00029 mmol/L, 0.00071mmol/L, 0.00359mmol/L, 0.00719mmol/L, 0.01438mmol/L, 0.02875mmol/L, 0.04633mmol/L, 0.06387mmol/L, 0.08137mmol/L, 0.11628mmol/L, 0.15105mmol/L, 0.20295mmol/L, 0.25455mmol/L, 0.30586mmol/L, 0.34023mmol/L, 0.40876 mmol/L) for 1min, under 250nm excitation fluorescence emission spectrum was recorded.
As shown in figure 1, csPbCl is prepared by adopting polyethylene glycol with good biocompatibility as a surface coating material 3 :Mn 2 + PEG nano grain diameter is uniform, csPbCl 3 :Mn 2+ Perovskite quantum dots are coated in PEG crystal nanocrystals, thus greatly improving CsPbCl 3 :Mn 2+ Fluorescence of perovskite quantum dots in waterLight stability. As shown in FIG. 2, csPbCl 3 :Mn 2+ After the PEG nanocrystalline is stored in water for 25 days, the fluorescence intensity is still more than 40% of the initial intensity, and after the PEG nanocrystalline is stored in water for 33 days, the fluorescence intensity is still 20% of the initial intensity. As shown in FIG. 3, csPbCl with good fluorescence stability 3 :Mn 2+ PEG nanocrystals were used as fluorescent probes for detection of 4-NP in water. The fluorescence intensity of the nanocrystals gradually decreased with increasing 4-NP concentration. As shown in FIG. 4, csPbCl 3 :Mn 2+ The relationship between the fluorescence intensity of the PEG nanocrystalline and the concentration of 4-NP accords with a Stern-Volmer equation, and can be represented by a formula I 0 /I=1+K sv C 4-NP Represented by, wherein I and I 0 CsPbCl with and without 4-NP, respectively 3 :Mn 2+ Fluorescence intensity of PEG nanocrystals. K (K) sv For the Stern-Volmer constant related to quenching efficiency, C 4-NP Is the molar concentration of 4-NP. Emission peak intensity ratio I in the range from 0.00029mmol/L to 0.40876mmol/L at 400nm and 590nm 0 A good linear relationship between I and 4-NP concentration (R 2 = 0.98224 and 0.98823), the linear equations fitted are I 0 /I (400nm) =1.0683+4.2545C 4-NP And I 0 /I (590nm) =1.1235+5.3868C 4-NP . Wherein K is sv 4.2545 ×10 respectively 3 And 5.3868 ×10 3 . Thus, csPbCl is utilized 3 :Mn 2+ The fluorescence intensity of the PEG nano crystal phase can be used for quantitative detection of 4-NP concentration in water, and the detection range is wide. The detection limit for detecting the concentration of 4-NP in the method of the present invention was very low, and the detection Limit (LOD) values calculated by the 3. Sigma/K formula were 0.40563. Mu.M (400 nm) and 0.36362. Mu.M (590 nm), respectively. The method has wide linear range and low LOD, and has good potential in the measurement of 4-NP in a water sample. As shown in FIG. 5, in CsPbCl 3 :Mn 2+ Aqueous PEG nanocrystalline solution, adding other interfering ions (K + ,Na + ,Ca 2+ ,Cu 2+ ,Mg 2+ ,Zn 2+ ,Fe 2+ ) Thereafter, at the same concentration (7.5. Mu.g/mL), 4-NP and interfering metal ions were reacted with CsPbCl, respectively 3 :Mn 2+ After the PEG nanocrystalline reaction, only 4-NP pairs CsPbCl3:Mn 2+ Fluorescence of PEG nanocrystals is evidentQuenching, the detection of 4-NP is not affected by the presence of metal ions. Thus, even in the presence of interfering compounds, csPbCl 3 :Mn 2+ PEG nanocrystals also have very high selectivity to 4-NP.
Claims (6)
1. CsPbCl 3 :Mn 2+ The method for detecting 4-nitrophenol in water by PEG nanocrystalline is characterized by comprising the following specific processes:
(1) Ligand-assisted reprecipitation method for synthesizing CsPbCl 3 :Mn 2+ PEG nanocrystals: pbCl is added 2 、MnCl 2 And polyethylene glycol PEG dissolved inN,NAdding oleic acid, oleylamine and concentrated HCl into dimethylformamide, stirring to obtain pale green precursor solution, adding the precursor solution into cesium acetate, oleic acid and xylene mixed solution under stirring, centrifuging after reaction to remove supernatant, adding toluene into precipitate, dispersing with ultrasound, centrifuging, and collecting precipitate to obtain CsPbCl 3 :Mn 2+ PEG nanocrystals; (2) The obtained CsPbCl 3 :Mn 2+ PEG nanocrystals were dispersed in deionized water, followed by CsPbCl 3 :Mn 2+ The PEG nanocrystalline solution is diluted into a hydrochloric acid diluted solution with the pH value of 1 and then is used for detecting 4-nitrophenol in water under the excitation of 250nm fluorescence.
2. A CsPbCl according to claim 1 3 :Mn 2+ The method for detecting 4-nitrophenol in water by PEG nanocrystalline is characterized by comprising the following specific steps: (1) Will be 0.25mmolPbCl 2 、0.25mmolMnCl 2 And 40mg polyethylene glycol PEG dissolved in 5mLN,NAdding 0.5mL of oleic acid and 0.5mL of oleylamine into dimethylformamide, adding 0.5mL of concentrated HCl, stirring to obtain a pale green precursor solution, injecting 1mL of precursor solution into a mixed solution containing 0.05mmol of cesium acetate, 1mL of oleic acid and 5mL of xylene under stirring, reacting for 30-38s, irradiating with an ultraviolet lamp to observe bright orange fluorescence, centrifuging the obtained sample, removing supernatant, adding 3mL of toluene into the precipitate, ultrasonically dispersing, and centrifuging to collect the precipitate to obtain CsPbCl 3 :Mn 2+ PEG nanocrystals; (2) Will be collected toCsPbCl of (C) 3 :Mn 2+ PEG nanocrystals were dispersed in 2mL deionized water to form CsPbCl 3 :Mn 2+ 100 mu L CsPbCl is measured out of PEG nanocrystalline aqueous solution 3 :Mn 2+ The PEG nanocrystalline aqueous solution is diluted into 3mL of hydrochloric acid diluted solution with pH value of 1 for detecting 4-nitrophenol in water.
3. A CsPbCl according to claim 2 3 :Mn 2+ The method for detecting 4-nitrophenol in water by PEG nanocrystalline is characterized in that: in the step (1), 1mL of the precursor solution was injected into a mixed solution containing 0.05mmol of cesium acetate, 1mL of oleic acid and 5mL of xylene with stirring at 1700-2000 r/min.
4. A CsPbCl according to claim 2 or 3 3 :Mn 2+ The method for detecting 4-nitrophenol in water by PEG nanocrystalline is characterized in that: and (3) centrifuging the sample obtained in the step (1) at 9000-10000r/min for 10-15min.
5. A CsPbCl according to claim 4 3 :Mn 2+ The method for detecting 4-nitrophenol in water by PEG nanocrystalline is characterized in that: in the step (1), 3mL of toluene is added into the sediment, ultrasonic dispersion is carried out by using ultrasonic wave with the frequency of 40KHz, and the sediment is collected by centrifugation for 10-15min at 9000-10000 r/min.
6. A CsPbCl according to claim 1 or 5 3 :Mn 2+ The method for detecting 4-nitrophenol in water by PEG nanocrystalline is characterized in that: csPbCl in the step (2) 3 :Mn 2+ The concentration range of 4-nitrophenol in the PEG nanocrystalline detection water is 0.00029-0.40876mmol/L.
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